Alkyl N-arylsulfenyl-N-diaryloxy-phosphinylmethylglycinates

ABSTRACT

This disclosure relaes to arylsulfenyl derivatives of benzyl and aryl esters of N-phosphonomethylglycines. This disclosure further relates to herbicidal compositions containing arylsulfenyl derivatives of benzyl and aryl esters of N-phosphonomethylglycines, to the use thereof, and to herbicidal methods employing such compounds and compositions.

This is a division of application Ser. No. 222,213, filed Jan. 2, 1981,now U.S. Pat. No. 4,395,374.

This invention relates to arylsulfenyl derivatives of benzyl and arylesters of N-phosphonomethylglycines. This invention further relates toherbicidal compositions containing arylsulfenyl derivatives of benzyland aryl esters of N-phosphonomethylglycines to the use thereof and toherbicidal methods employing such compounds to plant growth regulatorcompositions, and to the use thereof.

U.S. Pat. No. 4,120,689 issued to Gerard A. Dutra on Oct. 17, 1978describes alkyl-[di(benzyl) or di(aryl)]esters ofN-phosphonomethylglycine which are produced by the reaction of adibenzyl or diaryl phosphite with an N-methylene alkyl glycinate trimer.These esters and the hydrolysis products thereof containing at least onebenzyloxy or aryloxy group bonded to phosphorus are compounds disclosedas having the formula ##STR1## wherein R is a member of the groupconsisting of phenyl, benzyl, naphthyl, biphenylyl, and phenyl, benzylor naphthyl groups substituted with from 1 to 3 groups selected from theclass consisting of hydroxyl, lower alkyl, lower alkoxy, loweralkylthio, trifluoromethyl, carbo (lower alkoxy), nitro or halo; R₁ ishydrogen or an R group, and R₂ is a lower alkyl group or hydrogen, andthe strong acid salts of the compounds wherein neither R₁ or R₂ is H.The aforementioned compounds are disclosed as useful as post-emergentherbicides.

The compounds of the present invention are represented by the formula##STR2## wherein R is phenyl, naphthyl, biphenylyl, benzyl, or naphthyl,biphenylyl, benzyl or phenyl substituted with from one to threesubstituents independently selected from the group consisting ofhydrogen, lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl,alkoxycarbonyl, methylenedioxy, cyano, nitro and halogen; R₁ isnaphthyl, phenyl or phenyl substituted with from one to threesubstituents independently selected from the group consisting ofhydrogen, lower alkyl, lower alkoxy, halogen, trifluoromethyl and nitro;R₂ is selected from the group consisting of lower alkyl and loweraralkyl.

It is preferred that R is phenyl or substituted phenyl. Also, it ispreferred that the substituted phenyl groups represented by R and R₁contain one or two substituents.

Illustrative of the substituted phenyl groups which R and R₁ representare mono-substituted phenyl wherein the substituent is in the ortho,meta or para position, for example, methylphenyl, butylphenyl,methoxyphenyl, butoxyphenyl, fluorophenyl, chlorophenyl, bromophenyl,iodophenyl, trifluoromethylphenyl, nitrophenyl, methylthiophenyl,butylthiophenyl, cyanophenyl, ethoxycarbonylphenyl, and the like, anddi- and tri-substituted phenyl groups wherein the substituents are thesame or different and are located in the 2, 3, 4, 5 or 6 positions ofthe phenyl ring, for example, dichlorophenyl, dinitrophenyl,dimethylphenyl, methylchlorophenyl, ethylfluorophenyl, dibutoxyphenyl,butylnitrophenyl, methylthiochlorophenyl, di(ethylthio)phenyl,trimethylphenyl, trichlorophenyl, tributylphenyl, ethyldichlorophenyl,4-chloro-3-methylphenyl and the like.

Groups representative of the substituted biphenylyl groups representedby R include methylbiphenylyl, nitrobiphenylyl, bromobiphenylyl,dimethylbiphenylyl, difluorobiphenylyl, trimethylbiphenylyl and thelike.

As employed throughout the claims and description, the term "loweralkyl" designates alkyl radicals which have up to four carbon atoms in astraight or branched chain, such as methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl and t-butyl.

As employed throughout the claims and description, the term "loweralkoxy" designates alkoxy radicals which have 1 to 4 carbon atoms in astraight or branched chain such as methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, sec-butoxy and t-butoxy.

Illustrative lower aralkyl include benzyl and phenylethyl.

In accordance with the present invention, the benzyl and aryl esters ofN-phosphonomethylglycines of formula (I) are prepared by reacting acompound of the formula ##STR3## wherein R and R₂ are defined as above,in an aprotic solvent, with a compound of the formula

    R.sub.1 --S--Cl                                            (III)

wherein R₁ is as defined above, in the presence of a hydrogen chlorideacceptor.

Typical compounds of formula (III) are aryl sulfenyl chlorides. Themethod employed for the preparation of aryl sulfenyl chlorides offormula (III) is based on the quantitative reaction of aryl thiols withN-chloro-succinimide to give a reagent solution which comprisesarylsulfenyl chloride as well as the "inert" co-product succinimide. Thereagent solution is stirred at room temperature of about 25° C. fromabout 1 to 3 hours, cooled in an ice bath, and a solvent such as carbontetrachloride is added to precipitate the succinimide. The resultingmixture is then filtered under nitrogen and transferred to theglycinate, amine and toluene solution. Typically aryl sulfenyl chlorideis prepared in situ employing the aforedescribed methods areparticularly described in "Chlorosulfenylation-DehydrochlorinationReactions. New and Improved Methodology for the Synthesis of UnsaturatedAryl Sulfides and Aryl Sulfones" by Hopkins, Paul B. and Fuchs, PhilipL., Department of Chemistry, Purdue University, West Lafayette, Ind.47907, J. Org. Chem., Vol. 43, No. 6, (1978) pages 1208-1217, theteachings of which are incorporated herein in their entirety byreference.

It has been found that the temperature employed for the reaction of arylsulfenyl chloride with compounds of formula (II) is in the range fromabout 0° to about 100° C. For ease of reaction and recovery of product,it is preferred to conduct the reaction in the range from about 10° toabout 30° C.

In preparing the compounds of formula (I), the molar ratio of reactantsis not narrowly critical. For best results, however, for each mole of acompound of formula (II), one should employ about one mole of an arylsulfenyl chloride of formula (III) to produce one mole of a compound offormula (I). However, it is preferred to employ an excess of an arylsulfenyl chloride of formula (III) for ease of reaction and maximumyield of product.

The hydrogen chloride acceptor is preferably employed in excess ofstoichiometric requirements to insure completeness of reaction.

The hydrogen chloride acceptor is an amine, preferably a tertiary amine,which is insert to reactants employed and products formed. Examples ofsuitable tertiary amine hydrogen chloride acceptors includetrimethylamine, triethylamine, tributylamine, trihexylamine,1,5-diazabicyclo-[5.4.0]-undec-5-ene, pyridine, quinoline and the like.Triethylamine is the preferred hydrogen chloride acceptor.

Due to the highly reactive nature of the various reactants andintermediates, the process of the present invention should be conductedin an aprotic solvent under essentially anhydrous conditions.Illustrative aprotic solvents employable in the process of thisinvention include benzene, toluene, tetrahydrofuran, cyclohexane,methylcyclohexane, hexane, octane, dioxane, ethyl ether and the like,although toluene is the preferred aprotic solvent.

While the processes of this invention can be conducted at atmospheric,sub-atmospheric or super-atmospheric pressure, for convenience andeconomy it is generally preferred to conduct these processes atatmospheric pressure.

The following illustrative, non-limiting examples will serve to furtherdemonstrate the manner in which specific compounds within the scope ofthis invention can be prepared and used. In the examples, all parts areparts by weight unless otherwise expressly stated.

EXAMPLE 1

A benzene solution (250 ml) of commercially available 2,4dinitrophenylsulfenyl chloride (12.8 g, 0.053 mole) was added dropwiseto a benzene solution (250 ml) of ethylN-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate (21.5 g, 0.050 mole)and triethylamine (20.2 g, 0.20 mole) at a temperature of 25° C. to forma reaction mixture. This reaction mixture was stirred for 6 days andthen filtered to remove solids. The mother liquor was concentrated to adark oil whch was then titurated with ethyl ether and decanted. Theethyl ether solution was then concentrated to give a dark oil (A).

A first portion of dark oil (A) was purified by column chromatographyover silica gel eluting with cyclohexane/ethyl acetate to give ethylN-(2,4-dinitrophenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate(3.5 g, 29% yield) as a hydrated yellow oil, n_(D) ²⁵ 1.5898.

Anal. Calculated for C₂₅ H₂₆ N₃ O₁₁ PS.H₂ O: C 48.00; H 4.51; N 6.72.Found: C 47.75; H 4.36; N 6.30.

EXAMPLE 2

The remaining portion of oil (A) prepared in Example 1 was stirred inether/Benzene, allowed to stand 7 days and the solids which formed werecollected by filtration. These solids were stirred in CHCl₃, filtered toremove insolubles, concentrated to an oil, stirred in benzene, filteredto remove insolubles. Yellow crystals formed in this benzene solution ina few days upon standing. The yellow solids were collected by filtrationand washed with ethyl acetate to give ethylN-(2,4-dinitrophenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinateyield as a yellow solid, m.p. 124°-125° C. A proton NMR indicated thatthe structure of these yellow solids was identical to the structure ofthe hydrated oil of Example 1.

Anal. Calculated for C₂₅ H₂₆ N₃ O₁₁ PS: C 49.43; H 4.31; N 6.92. Found:C 49.56; H 4.22; N 6.92.

EXAMPLE 3

2,4-Dinitrophenylsulfenyl chloride (5 grams, 0.021 moles) in benzene wasadded to a solution comprising ethylN-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate (8 grams, 0.0195moles) and triethylamine (2.3 grams, 0.023 moles) in 100 ml. of toluene.The resulting composition turned a brown color and was stirred for 13days at 25° C. whereby a yellow solid was formed. This solid was removedby filtration. The resulting filtrate was concentrated to a brown oil.This oil was extracted with diethyl ether. ³¹ P NMR spectral analysis ofthe ether extracts indicated a mixture of the desired sulfenamide andunreacted starting material. This crude product was adsorbed onto silicagel and purified by medium pressure liquid chromatography eluting with60:40 cyclohexane/ethyl acetate to give ethyl N-(2,4dinitrophenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinateas a yellow solid (1.3 grams, 11% yield) m.p. 112°-116° C.

Anal. Calculated for C₂₅ N₂₆ N₃ O₁₁ PS: C, 49.43; H, 4.31; N, 6.92; S,5.28. Found: C, 49.55; H, 4.36; N, 6.89; S, 5.26.

In the following Examples 4-11, the aryl sulfenyl chloride employed as areactant was generated in situ according to the aforedescribed methodsdisclosed in J. Org. Chem. supra.

EXAMPLE 4

4-Methylphenylsulfenyl chloride (3.67 grams, 0.023 moles) previouslygenerated in situ was added to a solution of methylN-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate (9.2 grams, 0.023moles) and triethylamine (2.3 grams, 0.023 moles) in 100 ml. of tolueneto form a reaction mixture. The mixture was stirred for 16 hours at atemperature of 25° C., filtered and concentrated to give a dark orangeoil. Purification of the dark orange oil by medium pressurechromatography eluting with 50:50 cyclohexane/ethyl acetate gave MethylN-(4-methyl-phenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinateas an orange oil (7.3 grams, 46% yield), n_(D) ²³ 1.5639.

Anal. Calculated for C₂₅ H₂₈ NO₇ PS: C, 58.02; H, 5.45; N, 2.71. Found:C, 58.22; H, 5.48; N, 2.66.

EXAMPLE 5

To a solution of methyl N-[diphenoxyphosphinylmethyl]glycinate (6.5grams, 0.02 moles) and triethylamine (2.0 grams, 0.02 moles) in 100 ml.of toluene at 25° C. was added 4-methylphenylsulfenyl chloride (3.1grams, 0.02 moles) previously generated in situ to form a reactionmixture. The reaction mixture was stirred for 25 hours at a temperatureof 25° C. and was then filtered forming a toluene filtrate. Theresulting toluene filtrate was washed successively with cold 10% sodiumhydroxide, cold water and then dried over magnesium sulfate, filtered,and concentrated on a rotary evaporator to give a clear yellow oil whichcrystallized on standing to give methylN-[(4-methylphenyl)thio]-N-[diphenoxyphosphinyl]methyl glycinate as alight yellow solid (7.2 grams, 89%), m.p. 40°-47° C.

Calc'd. for C₂₃ H₂₄ NO₅ PS: C, 60.38; H, 5.29; N, 3.06; S, 7.01. Found:C, 60.37; H, 5.32; N, 3.05; S, 7.07.

EXAMPLE 6

To a solution of ethylN-[(bis-4-chloro-3-methylphenoxy)phosphinylmethyl]glycinate (8.2 grams,0.018 moles) and triethylamine (1.9 grams, 0.018 moles) in 100 ml. oftoluene at 0° C. was added 4-methylphenylsulfenyl chloride (2.9 grams,0.018 moles) previously generated in situ to form a reaction mixture.The reaction mixture was allowed to warm to 25° C. and stirred for 16hours. The reaction mixture was filtered. The resulting toluene filtratewas washed successively with cold 10% sodium hydroxide, cold water,dried over magnesium sulfate, filtered and concentrated on a rotaryevaporator to give a crude product. 5.0 grams of the crude product wasadsorbed onto 10 grams of oven-dried silica gel and then was extractedoff by stirring in hot ethyl acetate to form an ethyl acetate mixture.The ethyl acetate mixture was filtered and concentrated to give a yellowoil which was impure by thin layer chromatography. This yellow oil wastaken up in diethyl ether and washed successively again with cold 10%sodium hydroxide, cold water, dried over magnesium sulfate, filtered andconcentrated to giveethyl-N-(4-methylphenylthio)-N-[bis-(4-chloro-3-methyl-phenoxy)phosphinylmethyl]glycinateas a white solid, (2.0 grams, 19% yield), m.p. 55°-58° C. An additional3.1 grams of product could be obtained by crystallizing the remaining 5grams of crude product from cold diethyl ether. Total yield was 5.1grams (49% yield).

Anal. Calculated for C₂₆ H₂₈ Cl₂ NO₅ PS: C, 54.94; H, 4.97; N, 2.46; S,5.64. Found: C, 54.66; H, 5.00; N, 2.41; S, 5.73.

EXAMPLE 7

4-chlorophenylsulfenyl chloride (5.4 grams, 0.03 mole) was prepared insitu using the aforedescribed literature methods. The sulfenyl chloridesolution was transferred under nitrogen into a cold toluene solution(100 ml) of methyl N-[(bis-2-methoxyphenoxy)phosphinylmethyl]glycinate(8.3 grams, 0.021 mole) and triethylamine (3.0 grams, 0.030 mole) toform a reaction mixture. The reaction mixture was allowed to warm to atemperature of 25° C. and stirred for 16 hours. The reaction mixture wasthen filtered to remove triethylamine hydrochloride. The toluenefiltrate was washed with equal volumes of cold 10% aqueous sodiumhydroxide and cold water, dried over magnesium sulfate and then thedried material was purified by medium pressure liquid chromotography onsilica gel eluting with 60% cyclohexane, 40% ethylacetate to givemethyl-N-(4-chlorophenylthio)-N-[(bis-2-methoxyphenoxy)phosphinyl-methyl]glycinateas a yellow semi-solid (2.8 grams, 25% yield).

Anal. Calculated for C₂₄ H₂₅ ClNO₇ PS: C, b 53.58; H, 4.68; N, 2.60; S,5.96. Found: C, 53.43; H, 4.72; N, 2.66; S, 6.03.

EXAMPLE 8

4-methylphenylsulfenyl chloride (4.0 grams, 0.025 mole) was generated insitu using the aforedescribed literature methods. This solution was thentransferred under nitrogen into a cold toluene solution (100 ml) ofphenylmethyl-N-[diphenoxy)phosphinylmethyl]-glycinate (8.6 grams, 0.021mole) and triethylamine (2.5 grams, 0.025 mole) to form a reactionmixture. The reaction mixture was allowed to warm to a removetriethylamine hydrochloride. The resulting toluene filtrate was washedwith equal volumes of cold 10% aqueous sodium hydroxide and cold water,dried over magnesium sulfate and then the washed material was purifiedby medium pressure liquid chromatography on silica gel eluting with 60%cyclohexane, 40% ethyl acetate to give phenylmethylN-(4-methylphenylthio)-N-[diphenoxyphosphinylmethyl]glycinate as a whitesolid mp 108°-111° C. (1.1 grams, 10%).

Anal. Calculated for C₂₉ H₂₈ NO₅ PS: C, 65.28; H, 5.29; N, 2.63; S,6.01. Found: C, 65.31; H, 5.31; N, 2.63; S, 5.96.

EXAMPLE 9

3-Trifluoromethylphenylsulfenyl chloride (7.4 grams, 0.035 mole) wasgenerated in situ using the aforedescribed literature methods. Thissolution was transferred under nitrogen into a cold toluene solution(100 ml) of methyl-N-[diphenoxy)phosphinylmethyl]glycinate (11.6 grams,0.035 mole) and triethylamine (3.5 grams, 0.035 mole) to form a reactionmixture. The reaction mixture was allowed to warm to 25° C. slowly andstirred for 16 hours. The reaction mixture was then filtered to removetriethylamine hydrochloride. The resulting toluene filtrate was washedwith equal volumes of cold 10% aqueous sodium hydroxide and cold waterand dried over magnesium sulfate. The washed material was purified bymedium pressure liquid chromotography on silica gel, eluting with 70%cyclohexane, 40% ethyl acetate to givemethyl-N-(3-trifluoromethylphenylthio)-N-[diphenoxyphosphinylmethyl]glycinateas a light yellow oil (4.4 grams, 25% yield) n_(D) ²⁵.6° C. 1.5453.

Anal. Calculated for C₂₃ H₂₁ F₃ NO₅ PS: C, 54.01; H, 4.14; N, 2.74; S,6.27. Found: C, 54.13; H, 4.20; N, 2.68; S, 6.32.

EXAMPLE 10

4-methoxy-phenylsulfenyl chloride (5.2 grams, 0.03 mole) previouslyprepared in situ was added to a cooled solution of methyl N-[(bis4-methoxyphenoxy)phosphinylmethyl]glycinate (8.0 grams, 0.02 mole) andtriethylamine (5.0 grams, 0.03 mole) in toluene to form a reactionmixture. The reaction mixture was stirred for 3 hours, allowing thereaction mixture to slowly warm to a temperature of 25° C. andtriethylamine hydrochloride was removed by filtration. The resultingtoluene filtrate was washed with cold 10% aqueous NaOH followed by coldwater, dried over MgSO₄, filtered, and concentrated to yield 11 grams ofbrown oil. The brown oil was purified by medium pressure liquidchromotography on silica gel eluting with 60% cyclohexane, 40% ethylacetate to givemethyl-N-(4-methoxyphenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinateas a white solid, m.p. 66°-70° C. in 52% yield.

Anal. Calculated for C₂₅ H₂₈ NO₈ PS: C, 56.28; H, 5.29; N, 2.63; S,6.01. Found: C, 56.23; H, 5.30; N, 2.63; S, 6.02.

EXAMPLE 11

2-Naphthylsulfenyl chloride (5.8 grams, 0.030 mole) was generated byadding a solution of 2-naphthalenethiol (3.7 grams, 0.03 moles) inmethylene chloride to a slurry of N-chlorosuccinimide (4 grams, 0.030mole). The reaction mixture was stirred for 2 hours, cooled in an icebath, and carbon tetrachloride was added to precipitate all thesuccinimide which had formed. The mixture was then filtered undernitrogen into a solution of methylN-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate (7.7 grams, 0.02moles) and triethylamine (2.1 grams, 0.02 moles) in toluene at 0° C. toform a yellow reaction mixture. The yellow reaction mixture was stirredfor 16 hours and allowed to slowly warm to a temperature of 25° C. Theprecipitated triethylamine hydrochloride was removed by filtration. Theresulting toluene filtrate was washed with cold 10% aqueous NaOH andcold water, dried over MgSO₄, filtered and concentrated to give a pinksemi-solid. This pink semi-solid was purified by medium pressure liquidchromotography on silica gel eluting with 70% cyclohexane, 30%ethylacetate to give methyl-N-(2-naphthylthio)N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate as a yellow solid,m.p. 51°-54° C., in 11% yield.

Calc'd. for C₂₈ H₂₈ N₁ O₇ P₁ S₁ : C, 60.75; H, 5.10; N, 2.53; S, 5.79.Found: C, 60.93; H, 5.14; N, 2.70; S, 6.02.

EXAMPLE 12

The post-emergence herbicidal activity of the various compounds of thisinvention is demonstrated by greenhouse testing in the following manner.

A good grade of top soil is placed in aluminum pans having holes in thebottom and compacted to a depth of 0.95 to 1.27 cm. from the top of thepan. A predetermined number of seeds of each of several dicotyledonousand monocotyledonous annual plant species and/or vegetative propagulesfor the perennial plant species are placed on the soil and pressed intothe soil surface. The seeds and/or vegetative propagules are coveredwith soil and leveled. The pans are then placed on a sand bench in thegreenhouse and watered from below as needed.

After the plants reach the desired age (two to three weeks), each panexcept for the control pans is removed individually to a sprayingchamber and sprayed by means of an atomizer operating at a positive airpressure of approximately 1.46 kg/cm² absolute. The atomizer contains 6ml. of a solution or suspension of the chemical. In that 6 ml., is anamount of a cyclohexanone emulsifying agent mixture to give a spraysolution or suspension which contains about 0.4% by weight of theemulsifier. The spray solution or suspension contains a sufficientamount of the candidate chemical in order to give application ratescorresponding to those set forth in the tables. The spray solution isprepared by taking an aliquot of a 1.0% by weight stock solution orsuspension of the candidate chemical in an organic solvent such asacetone or tetrahydrofuran or in water.

The emulsifying agent employed is a mixture comprising 35 weight percentbutylamine dodecylbenzene sulfonate and 65 weight percent of a tall oilethylene oxide condensate having about 11 moles of ethylene oxide permole of tall oil. The pans are returned to the greenhouse and watered asbefore and the injury to the plants as compared to the control isobserved at approximately two and four weeks as indicated in the tablesunder WAT and the results recorded. In some instances, the two-weekobservations are omitted.

The post-emergence herbicidal activity index used in Tables I and II isas follows:

    ______________________________________                                        Plant Response  Index                                                         ______________________________________                                        0-24% control   0                                                             25-49% control  1                                                             50-74% control  2                                                             75-99% control  3                                                             100% control    4                                                             ______________________________________                                    

The plant species utilized in these tests are identified by letter inaccordance with the following legend:

    ______________________________________                                        A -- Canada Thistle*                                                                              K -- Barnyardgrass                                        B -- Cocklebur      L -- Soybean                                              C -- Velvetleaf     M -- Sugar Beet                                           D -- Morningglory   N -- Wheat                                                E -- Lambsquarters  O -- Rice                                                 F -- Smartweed      P -- Sorghum                                              G -- Yellow Nutsedge*                                                                             Q -- Wild Buckwheat                                       H -- Quackgrass*    R -- Hemp Sesbania                                        I -- Johnsongrass*  S -- Panicum Spp                                          J -- Downy Brome    T -- Crabgrass                                            ______________________________________                                         *Established from vegetative propagules.                                      A dash in the tables indicates that the particular species of plant was       absent in that test.                                                     

                                      TABLE I                                     __________________________________________________________________________    Compound of   Plant Species                                                   Example No.                                                                          WAT kg/h                                                                             A B C D  E F G H  I J K                                         __________________________________________________________________________    1      4   11.2                                                                             2 2 2 2  3 3 0 0  1 1 3                                         1      4   5.6                                                                              1 1 1 1  3 2 0 0  0 1 2                                         2      4   11.2                                                                             4 3 1 2  3 3 1 1  2 1 2                                         2      4   5.6                                                                              1 2 1 2  4 1 1 1  2 1 3                                         4      4   11.2                                                                             0 3 1 2  4 4 0 1  2 1 3                                         4      4   5.6                                                                              1 2 1 2  4 4 1 1  2 0 3                                         5      4   11.2                                                                             2 3 3 2  4 3 2 3  2 3 4                                         6      4   11.2                                                                             --                                                                              2 2 1  3 0 1 0  3 3 2                                         6      4   5.6                                                                              --                                                                              2 1 2  4 2 1 2  3 3 3                                         7      4   11.2                                                                             1 2 0 1  4 3 1 0  3 1 3                                         7      4   5.6                                                                              0 1 0 1  3 2 1 1  2 1 3                                         8      4   11.2                                                                             0 1 0 1  0 0 0 0  0 0 0                                         9      4   11.2                                                                             2 3 2 2  4 2 2 1  4 2 3                                         9      4   5.6                                                                              2 2 2 2  4 2 2 3  2 2 3                                         10     4   11.2                                                                             2 3 1 2  4 4 2 3  2 2 4                                         10     4   5.6                                                                              2 2 1 2  4 0 2 2  3 2 3                                         11     4   11.2                                                                             2 2 0 2  2 2 0 0  1 1 3                                         11     4   5.6                                                                              1 2 0 1  3 4 1 0  1 0 2                                         __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    Compound of   Plant Species                                                   Example No.                                                                          WAT kg/h                                                                             L M N O P B Q D R E F C J S K T                                 __________________________________________________________________________    1      4   5.6                                                                              1 1 1 0 3 2 1 2 1 1 1 1 1 2 2 3                                 1      4   1.12                                                                             1 0 0 0 1 1 0 1 0 0 0 0 0 1 1 2                                 2      4   5.6                                                                              3 2 1 2 3 2 1 2 1 1 2 1 2 3 2 3                                 2      4   1.12                                                                             1 1 1 0 2 1 1 1 0 1 1 0 0 1 2 2                                 4      4   5.6                                                                              2 3 3 3 3 3 4 3 4 --                                                                              3 2 3 4 4 --                                4      4   1.12                                                                             1 0 1 1 1 1 1 1 --                                                                              2 2 0 1 3 3 --                                4      2   0.28                                                                             0 0 0 0 0 0 0 0 3 1 1 0 0 0 0 --                                5      4   5.6                                                                              4 4 4 4 4 3 4 3 1 4 4 4 4 4 4 --                                5      4   1.12                                                                             1 2 2 0 3 2 2 1 0 3 2 1 2 3 3 --                                5      4   0.28                                                                             0 0 1 0 1 1 1 1 0 1 0 0 0 2 1 --                                6      4   5.6                                                                              3 4 4 3 3 4 3 2 2 3 4 4 4 4 3 --                                6      4   1.12                                                                             1 1 1 1 3 2 1 2 0 2 0 1 2 3 2 --                                6      4   0.28                                                                             0 0 0 0 0 1 1 1 0 3 4 0 0 2 2 --                                7      4   5.6                                                                              2 3 2 1 2 2 2 2 3 3 4 1 2 4 3 4                                 7      4   1.12                                                                             1 2 1 0 2 2 2 2 4 4 4 1 1 2 3 4                                 7      4   0.28                                                                             0 1 0 0 1 0 0 0 0 2 4 0 0 1 2 3                                 9      4   5.6                                                                              2 4 3 3 4 3 4 3 3 4 4 3 3 4 4 4                                 9      4   1.12                                                                             1 1 2 1 1 2 2 2 4 4 4 2 2 2 3 3                                 9      4   0.28                                                                             0 1 0 0 1 1 2 1 1 2 1 0 1 0 2 2                                 10     4   5.6                                                                              1 3 2 2 3 2 4 3 1 4 --                                                                              1 3 4 4 4                                 10     4   1.12                                                                             1 1 1 0 2 2 1 2 0 3 --                                                                              1 1 2 2 3                                 10     4   0.28                                                                             1 0 0 0 1 1 1 1 0 2 --                                                                              0 0 1 2 3                                 11     4   5.6                                                                              1 3 1 0 2 3 1 2 0 3 --                                                                              0 1 2 3 3                                 11     4   1.12                                                                             1 0 0 0 1 0 0 1 0 2 --                                                                              0 0 1 2 3                                 11     2   0.28                                                                             1 0 0 0 1 0 0 0 0 1 --                                                                              0 0 0 1 1                                 __________________________________________________________________________

From the test results presented in Tables I and II, it can be seen thatthe post-emergent herbicidal activity of the compounds of this inventionis, for the most part, general in nature. In certain specific instances,however, some selectivity is demonstrated. In this regard, it should berecognized that each individual plant species selected for the abovetests is a representative member of a recognized family of plantspecies.

EXAMPLE 13

The pre-emergent herbicidal activity of various compounds of thisinvention is demonstrated as follows.

A good grade of top soil is placed in aluminum pans and compacted to adepth of 0.95 to 1.27 cm. from the top of each pan. A predeterminednumber of seeds or vegetative propagules of each of several plantspecies are placed on top of the soil in each pan and then pressed down.Herbicidal compositions prepared as in the previous example are appliedby admixture with or incorporation in the top layer of soil.

In this example, the soil required to cover the seeds and propagules wasweighed and admixed with a herbicidal composition containing a knownamount of the active ingredient (compound of this invention). The panswere then filled with the admixture and leveled. Watering was carriedout by permitting the soil in the pans to absorb moisture throughapertures in the pan bottoms. The seed and propagule containing panswere placed on a wet sand bench and were maintained for approximatelytwo weeks under ordinary conditions of sunlight and watering. At the endof this period, the number of emerged plants of each species were notedand were compared to an untreated control. The data is given in TablesIII and IV.

The pre-emergent herbicidal activity index used below is based uponaverage percent control of each species as follows:

    ______________________________________                                        Percent Control  Index                                                        ______________________________________                                        0-24% control    0                                                            25-49% control   1                                                            50-74% control   2                                                            75-100% control  3                                                            ______________________________________                                    

Plant species in the tables are identified by the same code letters usedin the previous example.

                                      TABLE III                                   __________________________________________________________________________    Compound of   Plant Species                                                   Example No.                                                                          WAT kg/h                                                                             A B C D  E F G H  I J K                                         __________________________________________________________________________    4      2   11.2                                                                             3 1 0 0  0 0 1 1  2 2 3                                         7      2   11.2                                                                             0 0 0 0  0 0 0 2  1 2 2                                         8      2   11.2                                                                             2 0 0 0  0 0 0 0  0 0 0                                         9      2   11.2                                                                             2 0 0 0  3 1 0 0  2 2 1                                         10     2   11.2                                                                             3 0 1 0  0 --                                                                              1 1  2 0 1                                         __________________________________________________________________________     A dash in the tables indicates that that particular species of plant was      absent in that test.                                                     

                                      TABLE IV                                    __________________________________________________________________________    Compound of   Plant Species                                                   Example No.                                                                          WAT kg/h                                                                             L M N O P B Q D R E F C J S K T                                 __________________________________________________________________________    4      4   11.2                                                                             1 0 0 0 1 1 0 0 0 0 0 0 0 2 1 --                                __________________________________________________________________________     A dash in the tables indicates that that particular species of plant was      absent in that test.                                                     

From Tables III and IV, it can be seen that the pre-emergent herbicidalactivity demonstrated some selectivity.

The herbicidal compositions, including concentrates which requiredilution prior to application to the plants, of this invention generallycomprise from 5 to 95 parts by weight of at least one compound of thisinvention and from 5 to 95 parts by weight of an adjuvant in liquid orsolid form, for example, from about 0.25 to 25 parts by weight ofwetting agent, from about 0.25 to 25 parts by weight of a dispersant andfrom 4.5 to about 94.5 parts by weight of inert liquid extender, forexample, water, acetone, tetrahydrofuran, all parts being by weight ofthe total composition. Preferably, the compositions of this inventioncontain from 5 to 75 parts by weight of at least one compound of thisinvention, together with the adjuvants.

Where required, from about 0.1 to 2.0 parts by weight of the inertliquid extender can be replaced by a corrosion inhibitor such as ethanolmercaptan, sodium thiosulfate, dodecylmono or dimercaptan oranti-foaming agent such as a dimethylpolysiloxane, or both. Thecompositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers and conditioning agentsto provide compositions in the form of finely-divided particulatesolids, pellets, solutions, dispersions or emulsions. Thus, the activeingredient can be used with an adjuvant such as a finely-divided solid,a liquid of organic origin, water, a wetting agent, a dispersing agent,an emulsifying agent or any suitable combination of these.

The herbicidal compositions of this invention, particularly liquids andsoluble powders, preferably contain as a conditioning agent one or moresurface-active agents in amounts sufficient to render a givencomposition readily dispersible in water or in oil. The incorporation ofa surface-active agent into the compositions greatly enhances theirefficacy. By the term "surface-active agent", it is understood thatwetting agents, dispersing agents, suspending agents and emulsifyingagents are included therein. Anionic, cationic and nonionic agents canbe employed with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chainacid esters of sodium isothionate, esters of sodium sulfosuccinate,sulfated or sulfonated fatty acid esters petroleum sulfonates,sulfonated vegetable oils, polyoxyethylene derivatives of phenols andalkylphenols (particularly isooctylphenol and nonylphenol) andpolyoxyethylene derivatives of the mono-higher fatty acid esters ofhexitol anhydrides (e.g., sorbitan). Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin, sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polymethylenebisnaphthalenesulfonate and sodium N-methyl-N-(long chain acid)taurates.

The following list gives some illustrative herbicidal compositions ofthis invention. It is to be realized that the solvents and surfactantsare interchangeable in the composition.

    ______________________________________                                        1.  Ethyl N--(2,4-dinitrophenylthio)-N--                                                                    95     parts                                        [(bis-4 methoxyphenoxy)phosphinylmethyl]                                      glycinate as a hydrated oil                                                   Methanol                  5      parts                                    2.  Ethyl N--(2,4-dinitrophenylthio)-N--                                                                    95     parts                                        [(bis-4 methoxyphenoxy)phosphinylmethyl]                                      glycinate                                                                     Fumed silica              5      parts                                    3.  Methyl N--(4-methylphenylthio)-N--                                                                      90     parts                                        [(bis-4-methoxyphenoxy)phosphinyl]                                            glycinate                                                                     Calcium dodecylbenzene sulfonate/                                                                       10     parts                                        ethoxylated nonyl phenol blend                                            4.  Methyl N--[(Diphenoxyphosphinyl)]-                                                                      90     parts                                        methyl-N--[(4-methylphenyl)thio]                                              glycinate                                                                     Ethoxylated octyl phenol  10     parts                                    5.  Ethyl N--(4-methylphenylthio)-N--                                                                       90     parts                                        [bis-(4-chloro-3-methylphenoxy)                                               phosphinylethyl]glycinate                                                     Chloroform                5      parts                                        Ethoxylated dinonyl phenol                                                                              5      parts                                    6.  Methyl N--(4-chlorophenylthio)-N--                                                                      75     parts                                        [(bis-2-methoxyphenoxy)phosphinyl]                                            glycinate                                                                     Butanol                   25     parts                                    7.  Phenylmethyl N--(4-methylphenylthio)-                                                                   75     parts                                        N--[(bis-phenoxy)phosphinyl]                                                  glycinate                                                                     Sodium dioctylsulfosuccinate                                                                            1.25   parts                                        Calcium lignosulfonate    2.75   parts                                        Amorphous silica (synthetic)                                                                            21     parts                                    8.  Methyl N--(4-trifluoromethylphenyl-                                                                     75     parts                                        thio)-N--[(bis-phenoxy)phosphinyl-                                            methyl]glycinate                                                              Toluene                   15     parts                                        Ethoxylated cocoamine/calcium                                                                           10     parts                                        dodecylbenzene sulfonate blend                                            9.  Methyl N--(4-methoxyphenylthio)-N--                                                                     45     parts                                        [(bis-4-methoxyphenoxy)phosphinyl-                                            methyl]glycinate                                                              Methyl cellulose          0.3    parts                                        Silica aerogel            1.5    parts                                        Sodium lignosulfonate     3.5    parts                                        Sodium N--methyl-N--oleyltaurate(67%)                                                                   2.0    parts                                        Water                     47.7   parts                                    10. Methyl N--(2-naphthylthio)-N--                                                                          50     parts                                        [(bis-4-methoxyphenoxy)phosphinyl-                                            methyl]glycinate                                                              Dimethylformamide         50     parts                                    11. Ethyl N--(2,4-dinitrophenylthio)-N--                                                                    50     parts                                        [(bis-4 methoxyphenoxy)phosphinylmethyl]                                      glycinate as a hydrated oil                                                   Monochlorobenzene         40     parts                                        Isopropyl dodecylbenzene  10     parts                                        sulfonate/ethoxylated castor oil                                              blend                                                                     12. Ethyl N--(2,4-dinitrophenylthio)-N--                                                                    50     parts                                        [(bis-4 methoxyphenoxy)phosphinylmethyl]                                      glycinate                                                                     Dimethylsulfoxide         40     parts                                        Ethoxylated soybeanamine  10     parts                                    13. Methyl N--(4-methylphenylthio)-N--                                                                      50     parts                                        [(bis-4-methoxyphenoxy)phosphinyl]                                            glycinate                                                                     γ-butyrolactone     25     parts                                        Ethoxylated dodecyl phenol                                                                              25     parts                                    14. Methyl N--[(Diphenoxyphosphinyl)]-                                                                      50     parts                                        methyl-N--[(4-methylphenyl)thio]                                              glycinate                                                                     1,1,1-Trichloroethane     42     parts                                        Ethoxylated nonyl phenol  8      parts                                    15. Ethyl N--(4-methylphenylthio)-N--                                                                       25     parts                                        [bis-(4-chloro-3-methylphenoxy)                                               phosphinylmethyl]glycinate                                                    Chloroform                75     parts                                    16. Methyl N--(4-chlorophenylthio)-N--                                                                      25     parts                                        [(bis-2-methoxyphenoxy)phosphinyl]                                            glycinate                                                                     Chloroform                70     parts                                        Ethxylated tallow amine   5      parts                                    17. Phenylmethyl N--(4-methylphenylthio)-                                                                   10     parts                                        N--[(bis-phenoxy)phosphinyl]                                                  glycinate                                                                     Sodium lignosulfonate     3      parts                                        Sodium N--methyl-N--oleyltaurate(67%)                                                                   1      part                                         Kaolinite Clay            86     parts                                    18. Methyl N--(4-trifluoromethylphenyl-                                                                     10     parts                                        thio)-N--[(bis-phenoxy)phosphinyl-                                            methyl]glycinate                                                              Attapulgite granules      90     parts                                        (20-40 mesh)                                                              19. Methyl N--(4-methoxyphenylthio)-N--                                                                     10     parts                                        [(bis-4-methoxyphenoxy)phosphinyl-                                            methyl]glycinate                                                              Bentonite (powdered)      90     parts                                    20. Methyl N--(2-naphthylthio)-N--                                                                          10     parts                                        [(bis-4-methoxyphenoxy)phosphinyl-                                            methyl]glycinate                                                              Methanol                  80     parts                                        Polyoxypropylene-         10     parts                                        polyoxyethylene block                                                         copolymer                                                                 21. Ethyl N--(2,4-dinitrophenylthio)-N--                                                                    10     parts                                        [(bis-4 methoxyphenoxy)phosphinylmethyl]                                      glycinate as a hydrated oil                                                   Ethanol                   88     parts                                        Polyoxyethylene (20)      2      parts                                        sorbitanmonolaurate                                                       22. Ethyl N--(2,4-dinitrophenylthio)-N--                                                                    10     parts                                        [(bis-4 methoxyphenoxy)phosphinylmethyl]                                      glycinate                                                                     Isopropanol               72     parts                                        Polyoxyethylene sorbitan- 18     parts                                        monooleate                                                                23. Methyl N--(4-methylphenylthio)-N--                                                                      5      parts                                        [(bis-4-methoxyphenoxy)phosphinyl]                                            glycinate                                                                     Dimethylformamide         95     parts                                    24. Methyl N--[(Diphenoxyphosphinyl)]-                                                                      5      parts                                        methyl-N--[(4-methylphenyl)thio]                                              glycinate                                                                     Acetonitrile              90     parts                                        Ethoxylated tallow amine  5      parts                                    25. Ethyl N--(4-methylphenylthio)-N--                                                                       5      parts                                        [bis-(4-chloro-3-methylphenoxy)                                               phosphinylmethyl]glycinate                                                    Ethanol                   94     parts                                        Ethoxylated tallow amine  1      part                                     26. Methyl N--(4-chlorophenylthio)-N--                                                                      5      parts                                        [(bis-2-methoxyphenoxy)phosphinyl]                                            glycinate                                                                     Isopropanol               80     parts                                        Ethoxylated cocoamine     15     parts                                    ______________________________________                                    

Several compounds of this invention are useful as plant growthregulators as hereafter described in Example 14.

EXAMPLE 14

In determining the regulatory effects of the compounds of this inventionon sugarcane, it should be noted that the appropriate rate ofapplication can vary from about 0.12 kg/hectare to about 5.6 kg/hectare.

Depending upon local cultural practices in various areas around theworld, sugarcane is grown for from about 9 to about 30 months beforeharvest, and it is thus necessary to consider both the chronological ageand the maturity stage of the cane in rate determinations. Applicationof the treatment to the sugarcane is generally made from about 2 to 12weeks prior to the scheduled harvest date. Preferably, such applicationsare made from 3 to 10 weeks before said date.

In this example individual sugarcane stalks were treated with compoundsof this invention 4 and 5 weeks before harvest. To avoid samplingerrors, older cane, preferably from about 13 to about 23 months old, wasemployed in the tests. For each compound employed, at least 5 stalkswere employed, processed and the total values of pol percent cane andjuice purity obtained were for each stalk. An identical number ofuntreated sugarcane stalks of the same age were similarly processed toprovide a control. A comparison of the values obtained for the treatedcane with corresponding values of the control sample provided aconvenient means of determining the regulatory effectiveness of thesecompounds which is hereafter shown in Table IV.

The analyses were carried out by the press method developed by T.Tanimoto and reported in Hawaiian Planters' Record, Volume 57, pp.133-150 (1964). The data are expressed as Juice Purity and Pol PercentCane. Pol Percent Cane is defined as a polarimetric determination andequals the percentage of sucrose if it is the only substance in thesolution which will rotate the plane of polarized light. A determinationof Pol Percent Cane is considered by those skilled in the art as aneffective means of determining the sucrose content of sugarcane juice.

In order to convert a change in Pol Percent Cane into a correspondingchange in the quantity of sugar obtained, it is first necessary to knowthe average normal yield of sugar in the area under test. Here, thetests are carried out in a region where about 225 to 245 metric tons ofcane are harvested per hectare, and about 22.5 metric tons of sugar areobtained from this quantity of cane. With this average normal yield of22.5 metric tons per hectare, an increase of just 0.1 Pol Percent Canetranslates to an increase of about 225 kg of sugar per hectare.

In this example, about 38 mg. of a compound of this invention wasdissolved in about 0.3 ml. of water. This solution was then applied tothe whorl of each of the sugarcane stalks to be tested with theexception of the control stalks. At the time of application, internodenumber 13 on each stalk was marked as a reference point. At 4 and 5weeks after treatment (WAT), the sugarcane plants were harvested, andthe portion from the reference point to the shoot apex of each stalk ofa treated or untreated group was removed, combined and analyzed asdescribed. The results obtained were shown in Table IV.

                  TABLE IV                                                        ______________________________________                                                   4 WAT       5 WAT                                                             Juice  Pol %    Juice    Pol %                                                Purity Cane     Purity   Cane                                      ______________________________________                                        Treated      73.52    8.20     74.29  8.01                                    Compound (A)                                                                  Untreated    62.36    5.58     67.06  6.27                                    Treated      83.15    11.92    84.29  12.39                                   Compound (B)                                                                  Untreated    79.55    10.05    81.90  10.92                                   ______________________________________                                         Wherein compound (A) is ethylN--(2,4                                          dinitrophenylthioN--[(bis4-methoxy)phenoxyphosphinylmethyl]glycinate of       Example 2.                                                                    Wherein compound (B) is                                                       methylN--(4methyl-phenylthio)-N--methoxyphenoxy)phosphinyl]glycinate of       Example 4.                                                               

When operating in accordance with the present invention, effectiveamounts of the compounds or compositions of this invention are appliedto the plants, or the soil containing the plants, or the incorporatedinto aquatic media in any convenient fashion. The application of liquidand particulate solid compositions to plants or soil can be carried outby conventional methods, e.g., power dusters, boom and hand sprayers andspray dusters including conventional tractor mounted sprayers, portableknapsack sprayers, portable powdered sprayers and mist blowers. Thecompositions can also be applied from airplanes as a dust or a spraybecause of their effectiveness at low dosages. The application ofherbicidal compositions to aquatic plants is usually carried out byadding the compositions to the aquatic media in the area where controlof the aquatic plants is desired.

The application of an effective amount of the compounds or compositionsof this invention to the plant is essential and critical for thepractice of the present invention. The exact amount of active ingredientto be employed is dependent upon the response desired in the plant aswell as such other factors as the plant species and stage of developmentthereof, and the amount of rainfall as well as the specific glycineemployed. In foliar treatment for the control of vegetative growth, theactive ingredients are applied in amounts from about 0.112 to about 56.0or more kilograms per hectare. In pre-emergent treatments, the rate ofapplication can be from about 0.56 to about 22.4 or more kilograms perhectare. In applications for the control of aquatic plants, the activeingredients are applied in amounts of from about 0.01 parts per millionto about 1000 parts per million, based on the aquatic medium. Aneffective amount for phytotoxic or herbicidal control is that amountnecessary for overall or selective control, i.e., a phytotoxic orherbicidal amount. It is believed that one skilled in the art canreadily determine from the teachings of this specification, includingexamples, the approximate application rate.

There are several methods for applying liquid compositions of thisinvention to emerged plants. Such methods include the use of wipersystems whereby the plant to be treated is contacted with an absorbentmaterial containing the particular liquid composition, a portion ofwhich is thereby released onto the plant upon contact therewith. Suchwiper systems typically comprise a reservoir of the liquid compositioninto which a portion of the absorbent material is placed and is fedtherethrough. Generally, substances employable as absorbent materialinclude substances of any shape or form capable of absorbing the liquidcomposition and releasing a portion of the same upon contact with theplant. Typical absorbent materials include felt, foam rubber, cellulose,nylon, sponges, hemp, cotton, burlap, polyester over acrylic,combinations thereof and the like. Forms of absorbent material includerope, twine, string, cloths, carpets, combinations thereof and the like.These forms may be assembled in any manner desired including a pipe ropewick, a wedge rope wick, a multi-rope wick and the like.

In another application method, liquid compositions may be selectivelyapplied to weeds by the use of recirculating sprayer systems wherein therecirculating spray unit is mounted on a tractor or high clearancemobile equipment and the spray is directed horizontally onto the weedsgrowing over a crop. Spray not intercepted by the weeds is collected ina recovery chamber before contacting the crop and is reused. Rollerapplications may also be employed to apply liquid compositions to weedsgrowing over a crop.

In yet another application method, shielded applicators may be employedto direct the liquid composition in the form of a spray onto the weedswhile effectively shielding the crops from the spray.

These and other application methods for selectively applying liquidcompositions to weeds are discussed in detail in Innovative Methods ofPost-Emergence Weed Control, McWhorter C. G., Southern Weed ScienceSociety, 33rd Annual Meeting Proceedings, Jan. 15-17, 1980; AuburnUniversity Printing Service, Auburn, Ala. U.S.A., the teachings of whichare incorporated herein by reference in their entirety.

Another method of applying liquid compositions of this invention toplants includes controlled droplet application which is also known asthe ultra low-volume chemical application. Controlled dropletapplication involves the production of uniform or nearly uniform spraydrops of a predetermined size and the conveyance of these drops withnegligible evaporation to a spray target. In particular, this methodcomprises feeding spray solutions to a rotary atomizer comprising asmall disk with serrated edges that disperses liquid into droplets asthe disk spins. Different droplet sizes are produced by changingsolution flow rates to the spinning disk or changing the speed ofrotation of the disk.

The aforementioned and other methods for applying liquid compositions toplants are discussed in detail in "Rope Wick Applicator-Tool With AFuture", Dale, James E., pp. 3-4, "The Recirculating Sprayer andRoundup® Herbicide", Derting, Claude W., pp. 5-7, and "C.D.A. HerbicideApplication", McGarvey, Frank X., Weeds Today, Volume 11, Number 2, pp.8-9, Late Spring, 1980, 309 W. Clark St., Champaign, Ill., the teachingsof which are incorporated herein by reference in their entirety.

Other application methods include the electrodyn spray system whereinthe spray stem atomizes and propels electrically charged droplets alongthe thin lines in an electrical field set up between a high voltagepositively charged nozzle, the nozzles themselves, and the earth'starget crop. The afore-described spray system is discussed in detail inAg. Chem. Dealer/Applicator, Aug. 1980, pp. 29-30, British Pat. No.1,569,707 and British Patent Application No. 2,022,418. The teachings ofthese articles are incorporated herein in their entirety by reference.

Systems employing vertically disposed rollers may be employed such asthose disclosed in FIG. 9 of La Sacrerie Belge, June 1976, Vol. 95, p.224.

Additionally, another spray system comprises a box like structure whichencloses an undesired plant. When the undesired plant is sprayed vianozzles, the spray cannot drift into adjacent plants which are outsidethe box. The unused liquid composition is collected for re-use with apipe. The aforementioned apparatus and technique is discussed in detailin La Sacrerie Belge, Vol. 95, June 1976, pp. 222-223 and Le BetteravierNo. 778, July/August 1974, p. 10. The teachings of these articles areincorporated herein in their entirety by reference.

Applicators may be of the magic wand type as described in British Pat.No. 1,303,967 or of the glove type as described in British Pat. No.1,282,002. These applicators are discussed in British Pat. Nos.1,508,709 and 1,535,095 and British Patent Application No. 2,004,724,wherein rotatable elements such as rotatable drums covered with suitableabsorbent are employed.

Those of skill in the art will recognize that the physical propertiessuch as the particular size of any slurried or dissolved components ofthe aforementioned formulations will influence the selection of theparticular method for applying formulations to emerged plants as willthe intended use of the compounds of this invention.

Although this invention has been described with respect to specificmodifications, the details thereof are not to be construed aslimitations, for it will be apparent that various equivalents, changesand modifications may be resorted to without departing from the spiritand scope thereof and it is understood that such equivalent embodimentsare intended to be included herein.

What is claimed is:
 1. A herbicidal composition comprising an inertadjuvant and a herbicidally effective amount of a compound of theformula ##STR4## wherein R is phenyl, naphthyl, biphenylyl, benzyl ornaphthyl, biphenylyl, benzyl or phenyl substituted with from one tothree substituents independently selected from the group consisting ofhydrogen, lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl,methylenedioxy, cyano, nitro and halogen; R₁ is phenyl, naphthyl orphenyl substituted with from one to three substituents independentlyselected from the group consisting of hydrogen, lower alkyl, loweralkoxy, halogen, trifluoromethyl and nitro; and R₂ is selected from thegroup consisting of lower alkyl and lower "benzyl and phenyl alkyl". 2.A composition according to claim 1 wherein R is phenyl or substitutedphenyl.
 3. A composition according to claim 2 wherein R₁ is phenylsubstituted with from one to three substituents independently selectedfrom the group consisting of hydrogen, lower alkyl, nitro, lower alkoxy,halogen and trifluoromethyl.
 4. A composition according to claim 1wherein said compound is ethylN-(2,4-dinitrophenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.5. A composition according to claim 1 wherein said compound is methylN-(4-methylphenylthio)-N-[(bis-4-methoxyphenoxy)phosphinyl]glycinate. 6.A composition according to claim 1 wherein said compound is methylN-[(4-methylphenyl)thio]-N-diphenoxyphosphinylmethylglycinate.
 7. Acomposition according to claim 1 wherein said compound is ethylN-(4-methylphenylthio)-N-[bis(4-chloro-3-methylphenoxy)phosphinylmethyl]glycinate.8. A composition according to claim 1 wherein said compound is methylN-(4-chlorophenylthio)-N-[(bis-2-methoxyphenoxy)phosphinylmethyl]glycinate9. A composition according to claim 1 wherein said compound isphenylmethylN-(4-methylphenylthio)-N-[diphenoxyphosphinylmethyl]glycinate.
 10. Acomposition according to claim 1 wherein said compound is methylN-(3-trifluoromethylphenylthio)-N-[diphenoxyphosphinylmethyl]glycinate.11. A composition according to claim 1 wherein said compound is methylN-(4-methoxyphenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.12. A composition according to claim 1 wherein said compound is methylN-(2-naphthylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.13. A method of controlling undesired plants which comprises contactingsaid plants or plant growth medium with a herbicidal amount of acompound of the formula ##STR5## wherein R is phenyl, naphthyl,biphenylyl, benzyl or naphthyl, biphenylyl, benzyl or phenyl substitutedwith from one to three substituents independently selected from thegroup consisting of hydrogen, lower alkyl, lower alkoxy, loweralkylthio, trifluoromethyl, methylenedioxy, cyano, nitro and halogen; R₁is phenyl, naphthyl or phenyl substituted with from one to threesubstituents independently selected from the group consisting ofhydrogen, lower alkyl, lower alkoxy, halogen, trifluoromethyl and nitro;and R₂ is selected from the group consisting of lower alkyl and lowerbenzyl and phenyl lower alkyl.
 14. A method according to claim 13wherein R is phenyl or substituted phenyl.
 15. A method according toclaim 14 wherein R₁ is phenyl substituted with from one to threesubstituents independently selected from the group consisting ofhydrogen, lower alkyl, nitro, lower alkoxy, halogen and trifluoromethyl.16. A method according to claim 13 wherein said compound is ethylN-(2,4-dinitrophenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.17. A method according to claim 13 wherein said compound is methylN-(4-methylphenylthio)-N-[(bis-4-methoxyphenoxy)phosphinyl]glycinate.18. A method according to claim 13 wherein said compound is methylN-[(4-methylphenyl)thio]-N-diphenoxyphosphinylmethylglycinate.
 19. Amethod according to claim 13 wherein said compound is ethylN-(4-methylphenylthio)-N-[bis(4-chloro-3-methylphenoxy)phosphinylmethyl]glycinate.20. A method according to claim 13 wherein said compound is methylN-(4-chlorphenylthio)-N-[(bis-2-methoxyphenoxy)phosphinylmethyl]glycinate.21. A method according to claim 13 wherein said compound is phenylmethylN-(4-methylphenylthio)-N-[diphenoxyphosphinylmethyl]glycinate.
 22. Amethod according to claim 13 wherein said compound is methylN-(3-trifluoromethylphenylthio)-N-[diphenoxyphosphinylmethyl]glycinate.23. A method according to claim 13 wherein said compound is methylN-(4-methoxyphenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.24. A method according to claim 13 wherein said compound is methylN-(2-naphthylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.25. A method for increasing the sucrose content of sugar cane plantswhich comprises applying to said plants from about 2 to about 10 weeksprior to harvest an effective sucrose increasing amount of an compoundrepresented by the formula: ##STR6## wherein R is phenyl, naphthyl,biphenylyl, benzyl or naphthyl, biphenylyl, benzyl or phenyl substitutedwith from one to three substituents independently selected from thegroup consisting of hydrogen, lower alkyl, lower alkoxy, loweralkylthio, trifluoromethyl, methylenedioxy, cyano, nitro and halogen; R₁is phenyl, naphthyl or phenyl substituted with from one to threesubstituents independently selected from the group consisting ofhydrogen, lower alkyl, lower alkoxy, halogen, trifluoromethyl and nitro;and R₂ is selected from the group consisting of lower alkyl and loweraralkyl.
 26. A method according to claim 25 wherein R is phenyl orsubstituted phenyl.
 27. A method according to claim 26 wherein R₁ isphenyl substituted with from one to three substituents independentlyselected from the group consisting of hydrogen, lower alkyl, nitro,lower alkoxy, halogen and trifluoromethyl.
 28. A method according toclaim 25 wherein said compound is ethylN-(2,4-dinitrophenylthio)-N-[(bis-4-methoxyphenoxy)phosphinylmethyl]glycinate.29. A method according to claim 25 wherein said compound is methylN-(4-methylphenylthio)-N-[(bis-4-methoxyphenoxy)phosphinyl]glycinate.